EP0257888B2 - Dérivés du carbamate iodopropargyle, méthode de préparation et compositions fongicides contenant ces dérivés comme agents actifs - Google Patents

Dérivés du carbamate iodopropargyle, méthode de préparation et compositions fongicides contenant ces dérivés comme agents actifs Download PDF

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Publication number
EP0257888B2
EP0257888B2 EP87307016A EP87307016A EP0257888B2 EP 0257888 B2 EP0257888 B2 EP 0257888B2 EP 87307016 A EP87307016 A EP 87307016A EP 87307016 A EP87307016 A EP 87307016A EP 0257888 B2 EP0257888 B2 EP 0257888B2
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Prior art keywords
general formula
reaction
derivative represented
active ingredient
compound
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German (de)
English (en)
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EP0257888A3 (en
EP0257888A2 (fr
EP0257888B1 (fr
Inventor
Tomoyuki Kusaba
Junya Takahashi
Masayo Sugano
Tamon Uematsu
Yukio Oguri
Tomohiro Teramae
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups

Definitions

  • the present invention relates to an iodopropargyl carbamate derivative, its production and agricultural and horticultural fungicides containing it as an active ingredient.
  • Iodopropargyl carbamate in particular, N-phenyl substituted carbamate, derivatives as such are disclosed in GB-A-2138292, which describes their incorporation in a coating composition for controlling the growth of algae.
  • hitherto compounds on the market as fungicides for use in agriculture and horticulture are dithiocarbamate compounds such as Maneb and Mancozeb and phthalimide compounds such as Captan and Difolatan. These compounds have a wide antimicrobial activity and find wide application.
  • carbamate derivatives embodying the invention which contain an iodopargyl group are compounds having few problems, described above and excellent fungicidal activity.
  • the present invention provides a fungicidal composition which comprises as an active ingredient a fungicidally effective amount of a carbamate derivative represented by the general formula (I) (hereinafter referred to as present compound), wherein X, which when more than one X is present, may each be the same as or different from one another, represents a cyano, nitro, halogenated C1 ⁇ 3 alkyl.
  • a carbamate derivative represented by the general formula (I) hereinafter referred to as present compound
  • X which when more than one X is present, may each be the same as or different from one another, represents a cyano, nitro, halogenated C1 ⁇ 3 alkyl.
  • R1 and R2 which may be the same as or different from one another, represent a hydrogen atom or a methyl group
  • Y represents a hydrogen or chlorine atom
  • m represents an integer of from 1 to 5
  • n represents an integer of from 1 to 4, the sum of m and n being less than 6, and an inert carrier, and the use of such carbamate derivatives as a fungicide.
  • the compositions are useful as agricultural and horticultural fungicides for controlling pathogenic fungi.
  • the invention also provides a compound of the above formula (I), provided that when m is 1, n is zero and R1 and R2 each represents a hydrogen atom, then X is other than methoxy or ethoxy.
  • downy mildew of vegetables and Japanese radish Peronospora brassicae
  • downy mildew of spinach Peronospora spinaciae
  • downy mildew of tobacco Peronospora tabacina
  • downy mildew of cucumber Pseudoperonospora cubensis
  • downy mildew of grape Plasmopara viticola
  • downy mildew of dropwort Plasmopara nivea ), late blight of apple.
  • compositions more preferably contain a compound represented by the general formula, wherein X, which when more than one X is present may each be the same as or different from one another, represents a cyano, nitro, halogenated C1-C3 alkyl, C1-C12 alkoxy, C1-C4 alkoxy-substituted C1-C3 alkyl, C3-C5 alkynyloxy or halogenated C1-C4 alkoxy group, and m represents an integer of from 1 to 5, and particularly preferably a compound represented by the general formula, wherein X, which, when more than one X is present, may each be the same as or different from one another, represents a cyano, nitro, halogenated C1-C2 alkyl or C1-C5 alkoxy group, and m represents an integer of from 1 to 3.
  • X which when more than one X is present may each be the same as or different from one another, represents a cyano, nitro,
  • the present compounds are produced through the following representative synthetic routes.
  • This is a method of reacting a phenyl isocyanate derivative represented by the general formula (II) with an iodopropargyl alcohol derivative represented by the general formula (III).
  • the reaction temperature is normally from -lO° to lOO°C
  • the reaction time is normally from a moment to l2 hours.
  • the amount of the iodopropargyl alcohol derivative represented by the general formula (III) is from O.9 to 2 equivalents based on l equivalent of the phenyl isocyanate derivative represented by the general formula (II).
  • a reaction solvent is not always necessary, but generally the reaction is carried out in the presence of a solvent.
  • the solvent usable includes for example aromatic hydrocarbons (e.g. benzene, toluene), ethers (e.g. diethyl ether, tetrahydrofuran), halogenated hydrocarbons (e.g. dichloromethane, chloroform), and mixtures thereof.
  • a catalyst is not always necessary, but the reaction can be promoted by adding the catalyst.
  • the catalyst usable includes tertiary amines (e.g. pyridine, triethylamine, diethylaniline), tin compounds (e.g. tetra-n-butyltin, di-n-butyltin chloride), Lewis acids (e.g. boron trifluoride, aluminum chloride), etc.
  • reaction temperature is normally from -lO°C to room temperature
  • reaction time is normally from a moment to l2 hours.
  • This reaction is carried out in the presence of an acid-binding agent, and this agent includes for example tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, quinoline, etc.
  • the amount of the chlorocarbonylating agent is from O.9 to 2 equivalents based on l equivalent of the iodopropargyl alcohol derivative represented by the general formula (III), and that of the acid-binding agent is from O.9 to 2 equivalents based on l equivalent of the same.
  • the above reaction is carried out in the presence of a solvent
  • the solvent usable includes for example aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. dichloromethane, chloroform), etc.
  • the reaction temperature is normally from - lO° to lOO°C
  • the reaction time is normally from a moment to l2 hours.
  • This reaction is carried out in the presence or absence of an acid-binding agent, but generally, it is carried out in the presence of an acid-binding agent.
  • the agent usable includes for example tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), etc.
  • the amount of the aniline derivative represented by the general formula (V) is from O.9 to 2.O equivalents based on l equivalent of the chlorocarbonate derivative represented by the general formula (IV), and that of the acid-binding agent is from O.9 to 2.O equivalents based on l equivalent of the same.
  • the above reaction is carried out in the presence of a solvent
  • the solvent usable includes for example aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. dichloromethane, chloroform), etc.
  • reaction of the phenyl isocyanate derivative represented by the general formula (II) with the propargyl alcohol derivative represented by the general formula (VI) can be carried out according to Method A.
  • the alkali usable includes for example alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), and the iodinating agent includes for example iodine.
  • alkali metal hydroxides e.g. sodium hydroxide, potassium hydroxide
  • the iodinating agent includes for example iodine.
  • the reaction temperature is normally from -lO°C to room temperature
  • the reaction time is normally from l to l2 hours.
  • any of the amounts of the iodinating agent and alkali is from l to l.5 equivalents based on l equivalent of the carbamate derivative represented by the general formula (VIII).
  • reaction of the propargyl alcohol derivative represented by the general formula (VI) with the chlorocarbonylating agent, and that of the chlorocarbonate derivative represented by the general formula (VIII) with the aniline derivative represented by the general formula (V) can be carried out according to Method B.
  • the reaction of the carbamate derivative represented by the general formula (VII) with the iodinating agent is carried out in the similar manner to the iodination in Method C.
  • the reaction temperature is normally from - lO°C to room temperature
  • the reaction time is normally from a moment to l2 hours.
  • an acid-binding agent and the agent usable includes for example tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, quinoline, etc.
  • the amount of phenyl chloroformate represented by the formula (IX) is from O.9 to 2 equivalents based on l equivalent of the iodopropargyl alcohol derivative represented by the general formula (III), and that of the acid-binding agent is from O.9 to 2 equivalents based on l equivalent of the same.
  • the above reaction is carried out in the presence of a solvent
  • the solvent usable includes for example aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. dichloromethane, chloroform), etc.
  • the reaction temperature is normally from - lO° to lOO°C
  • the reaction time is normally from a moment to l2 hours.
  • This reaction is carried out in the presence or absence of an acid-binding agent, and generally, it is carried out in the presence of an acid-binding agent.
  • the agent usable includes for example tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, etc., alkaline metal hydride such as sodium hydride, etc.
  • the amount of the aniline derivative represented by the general formula (V) is from O.9 to 2.O equivalents based on l equivalent of the carbonate derivative represented by the general formula (X), and that of the acid-binding agent is from O.9 to l.5 equivalents based on l equivalent of the same.
  • the above reaction is carried out in the presence of a solvent
  • the solvent usable includes for example aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. dichloromethane, chloroform), etc.
  • the iodopropargyl alcohol derivative represented by the general formula (III) can be obtained by iodinating commercially available propargyl alcohol according to the method described in J. Am. Chem. Soc., lO2 , 4l93-4l98 (l98O).
  • the present compounds When used as an active ingredient for fungicides, they may be used as they are without adding any other ingredients. Generally, however, they are formulated before use into emulsifiable concentrates, wettable powders, suspension formulations, dusts, liquid formulations, etc. by mixing with inert carriers such as solid carriers, liquid carriers, surface active agents and other auxiliaries for formulation.
  • inert carriers such as solid carriers, liquid carriers, surface active agents and other auxiliaries for formulation.
  • the content of the present compounds, which are an active ingredient, in these preparations may be from O.l to 99.9%, preferably from l to 9O%.
  • the solid carriers include fine powders or granules of kaolin clay, attapulgite clay, bentonite, terra abla, pyrophyllite, talc, diatomaceous earth, calcite, corn stalk powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicon dioxide, etc.
  • the liquid carriers include aromatic hydrocarbons (e.g. xylene, methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol, cellosolve), ketones (e.g. acetone, cyclohexane, isophorone), vegetable oils (e.g.
  • the surface active agents used for emulsification, dispersion, wetting, etc. include anionic surface active agents such as the salt of alkyl sulfates, alkyl(aryl)sulfonates, dialkyl sulfosuccinates, the salt of polyoxyethylene alkylaryl ether phosphoric acid esters, naphthalene-sulfonic acid/formalin condensates, etc. and nonionic surface active agents such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc.
  • the auxiliaries for formulation include lignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.
  • a method for applying the present compounds as agricultural and horticultural fungicides includes for example foliar application, solid treatment, seed disinfection, etc., but any of the methods generally used by
  • the present compounds When the present compounds are used as an active ingredient for agricultural and horticultural fungicides, their dosage rate varies with crops and diseases aimed at, degree of outbreak of diseases, preparation forms, application methods, application time, weather conditions, etc., but it is generally from O.5 to 2OO g/are.
  • the emulsifiable concentrates, wettable powders, suspension formulations, liquid formulations, etc. are applied in dilution with water, the application concentration of the present compounds is from O.OO5 to O.5%, preferably from O.Ol to O.2%.
  • the dusts, granules, etc. are applied as they are without dilution.
  • the present compounds can be used as agricultural and horticultural fungicides for plow fields, paddy fields, orchards, tea gardens, pastures, turfs, etc., and also an increase in the fungicidal activity can be expected by using them in mixture with other agricultural and horticultural fungicides.
  • they can be used in mixture with insecticides, acaricides, nematocides, herbicides, plant growth regulators, fertilizers, etc.
  • the controlling activity was expressed in six stages described below, 5, 4, 3, 2, l, O, according to the condition of disease of test plants at the time of examination, i.e. the degrees of colony and infected area on the leaves, stems, etc., observed with the naked eyes.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (10)

  1. Composition fongicide qui contient, comme ingrédient actif, une quantité efficace sur le plan fongicide d'un composé représenté par la formule générale
    Figure imgb0039
     dans laquelle les restes X qui, quand plus d'un X est présent, peuvent être identiques ou différents les uns des autres, représentent un groupement cyano, nitro, alkyle en C₁-C₃ halogéné, alcoxy en C₁-C₁₂, (alcoxy en C₁-C₄)alKyle en C₁-C₃, alcynyloxy en C₃-C₅, ou alcoxy en C₁-C₄ halogéné, R¹ et R² qui peuvent être identiques ou différents l'un de l'autre, représentent un atome d'hydrogène ou un groupement méthyle, Y représente un atome de chlore, m représente un entier de 1 à 5, et n représente zéro ou un entier de 1 à 4, la somme de m et n étant inférieure à 6; et un support inerte.
  2. Composition selon la revendication 1, dans laquelle n est zéro et R¹ et R² représentent chacun un atome d'hydrogène.
  3. Composition selon la revendication 1, dans laquelle les restes X qui, quand il y a plus d'un X, peuvent être identiques ou différents les uns des autres, représentent un groupement cyano, nitro, alkyle en C₁-C₂ halogéné ou alcoxy en C₁-C₅, n est zéro, R¹ et R² représentent chacun un atome d'hydrogène et m représente un entier de 1 à 3.
  4. Utilisation d'un composé représenté par la formule générale I, donnée et définie dans la revendication 1, comme fongicide.
  5. Utilisation d'un composé représenté par la formule générale I, donnée et définie dans la revendication 1, pour lutter contre les champignons phytopathogènes.
  6. Procédé de lutte contre les champignons phytopathogènes, qui consiste à appliquer aux champignons phytopathogènes une quantité efficace sur le plan fongicide d'un composé représenté par la formule générale I, donnée et définie dans la revendication 1.
  7. Composé représenté par la formule générale
    Figure imgb0040
     dans laquelle X, Y, m, n, R¹ et R² sont tels que définis dans la revendication 1, à la condition que, quand m est 1, n est zéro et R¹ et R² représentent chacun un atome d'hydrogène, X soit alors autre qu'un groupement méthoxy ou éthoxy.
  8. Composé selon la revendication 7, dans lequel n est zéro et R¹ et R² représentent chacun un atome d'hydrogène.
  9. Composé selon la revendication 7, dans lequel les restes X qui, quand il y a plus d'un X, peuvent être identiques ou différents les uns des autres, représentent un groupement cyano, nitro, alkyle en C₁-C₂ halogéné ou alcoxy en C₁-C₅, n est zéro, R¹ et R² représentent chacun un atome d'hydrogène et m représente un entier de 1 à 3.
  10. Composé de formules
    Figure imgb0041
    Figure imgb0042
    Figure imgb0043
    Figure imgb0044
    Figure imgb0045
EP87307016A 1986-08-26 1987-08-07 Dérivés du carbamate iodopropargyle, méthode de préparation et compositions fongicides contenant ces dérivés comme agents actifs Expired - Lifetime EP0257888B2 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP200274/86 1986-08-26
JP20027486 1986-08-26
JP20027686 1986-08-26
JP200276/86 1986-08-26
JP30739086 1986-12-22
JP307390/86 1986-12-22
JP315812/86 1986-12-23
JP31581286 1986-12-23

Publications (4)

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EP0257888A2 EP0257888A2 (fr) 1988-03-02
EP0257888A3 EP0257888A3 (en) 1988-09-21
EP0257888B1 EP0257888B1 (fr) 1992-06-17
EP0257888B2 true EP0257888B2 (fr) 1995-07-19

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Country Status (12)

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US (1) US4841088A (fr)
EP (1) EP0257888B2 (fr)
JP (1) JP2533331B2 (fr)
KR (1) KR880002816A (fr)
AU (1) AU600297B2 (fr)
BR (1) BR8704318A (fr)
DE (2) DE3779836T4 (fr)
ES (1) ES2038667T5 (fr)
HU (1) HU202196B (fr)
IL (1) IL83520A (fr)
PL (1) PL151848B1 (fr)
TR (1) TR22991A (fr)

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US5209930A (en) * 1990-12-10 1993-05-11 Rohm And Haas Company Preparation and use of n-iodopropargyl oxycarbonyl amino acid esters and derivatives as antimicrobial agents
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CA2080540A1 (fr) * 1991-10-24 1993-04-25 Adam Chi-Tung Hsu Procede pour la preparation d'halopropargylcarbamates
WO1994002451A1 (fr) * 1992-07-24 1994-02-03 Troy Chemical Corporation Derives d'uree d'haloalkynyle, leur procede de production et compositions fongicides les contenant
EP0702670A1 (fr) * 1993-06-07 1996-03-27 Bayer Ag Iodopropargylcarbamates et leur utilisation comme biocides pour la protection des vegetaux et des materiaux
US5326899A (en) * 1993-06-14 1994-07-05 Rohm And Haas Company Process for preparation of iodopropargyl carbamates
US5321151A (en) * 1993-06-14 1994-06-14 Rohm And Haas Company Process for preparation of iodopropargyl carbamates
US5554784A (en) * 1994-07-08 1996-09-10 Gruening; Rainer Process for preparing iodoalkynylcarbamates having a low tendency of yellowing when exposed to light
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US5693849A (en) * 1996-10-30 1997-12-02 Troy Corporation Aqueous synthesis of iodopropargyl carbamate
US20050159625A1 (en) * 2004-01-19 2005-07-21 Coates John S. Alkoxylated amine and process therefor

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JPS646250A (en) 1989-01-10
EP0257888A3 (en) 1988-09-21
EP0257888A2 (fr) 1988-03-02
JP2533331B2 (ja) 1996-09-11
DE3779836T2 (de) 1993-01-28
KR880002816A (ko) 1988-05-11
US4841088A (en) 1989-06-20
AU7715287A (en) 1988-03-03
DE3779836T4 (de) 1995-03-30
DE3779836D1 (de) 1992-07-23
PL151848B1 (en) 1990-10-31
PL267441A1 (en) 1988-07-21
HU202196B (en) 1991-02-28
BR8704318A (pt) 1988-04-19
AU600297B2 (en) 1990-08-09
ES2038667T5 (es) 1995-09-16
IL83520A (en) 1992-05-25
EP0257888B1 (fr) 1992-06-17
HUT44910A (en) 1988-05-30
IL83520A0 (en) 1988-01-31
ES2038667T3 (es) 1993-08-01
TR22991A (tr) 1989-01-05

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